Poly(phenylene oxide)plastic compositions containing halogenated aryl flame retardants

ABSTRACT

1. A PLASTIC COMPOSITION CONTAINING POLY(PHENYLENE OXIDE) HAVING INCORPORATED THEREIN A FLAME RETARDANT WHICH IS A HALOGENATED ARYL COMPOUND HAVING THE FORMULA:   Z(M)-(A(I)-PHENYLENE)-M-R-M&#39;&#39;-(A(I&#39;&#39;)-PHENYLENE)-Z(M&#39;&#39;)   WHEREIN Z IS SELECTED FROM THE GROUP CONSISTING OF BROMINE OR CHLORINE; M AND M&#39;&#39; ARE INTEGERS HAVING A VALUE OF 1-5; I AND I&#39;&#39; ARE INTEGERS HAVING A VALUE OF 0-2; M AND M&#39;&#39; ARE EACH INDEPENDENT AND ARE SELECTED FROM THE GROUP CONSISTING OF OXYGEN, -NH-OR SULFUR WITH THE PROVISO THAT M AND M&#39;&#39; CANNOT CONCURRENTLY BE OXYGEN IN BOTH CASES; A IS SELECTED FROM THE GROUP CONSISTING OF CHLORINE, CYANO, NITRO, LOWER ALKOXY, LOWER ALKYL, FLUORINE, DIALKYLAMINO, PHENYL, HALO--PHENYL, BENZYL, OR HALO-BENZYL; AND R IS SELECTED FROM THE GROUP CONSISTING OF (A) KALYLENE GROUP HAVING FROM ONE TO SIX CARBON ATOMS (B) CH2-CH(OH)-CH2 (C)CH2-CH(CH2OH)-CH2 (CH2)W-O-(CH2)W WHERE W=1-6   -CH2-(X(N)-PHENYLENE)-CH2-   WHERE X=II, CL, BR N=4 (F)CH2-C(O)-CH2 (G)CH2-CH   -CH2-CH(-C6H5)-   -CH2-(CYCLOHEXYLENE)-CH2-   WHERE S=SATURATED RING.

United States Patent U.S. Cl. 260-453 R 29 Claims ABSTRACT OF THE DISCLOSURE Plastic compositions containing poly(phenylene oxide) and halogenated aryl compounds having the formula wherein Z is bromine or chlorine, in and m are integers having a value of 1-5, i and i are integers having a value of 0-2, R is herein defined, M and M are each independent and are from the group oxygen, NH- or sulfur with the proviso that M and M cannot concurrently be oxygen in both cases, and A is chlorine, cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl, or halo-benzyl.

This application is a continuation-in-part of copending application Ser. No. 260,240, filed June 6, 1972, now abandoned. The entire specification of this case, Ser. No. 260,240, is to be considered as incorporated herein by reference.

The prior art considered in conjunction with the preparation of this application is as follows: U.S. 2,130,990; U.S. 2,186,367; U.S. 2,329,033; U.S. 3,666,692; U.S. 3,686,320; U.S. 3,658,634; German Pat. No. 1,139,636; German Pat. No. 2,054,522; Japanese Pat. No. 72/14,500 as cited in Volume 77, Chemical Abstracts, column 153737k (1972); Chemical Abstracts, Volume 13, column 448 Chemical Abstracts, Volume 31, column 7045 and Journal of the Chemical Society, pages 2972-2976 (1963 All of these publications are to be considered as incorporated herein by reference.

The present invention relates to plastic compositions containing poly(phenylene oxide), (herein referred to as PPO), and certain halogenated aryl compounds (hereinafter defined) as flame retardants for said plastic compositions.

PPO plastics and utility thereof are known in the art as exemplified by Encyclopedia of Polymer Science and Technology, Vol. 10, pages 92-111, John Wiley & Sons, Inc., New York, 1969, and which publication is in toto incorporated herein by reference.

The need for flame retarding PPO plastics has also been recognized in the art as exemplified by Encyclopedia of Polymer Science and Technology, ibid., pages 100 and 1 03.

The resultant disadvantages in the utilization of various prior art materials as flame retardants for PPO include, without limitation, factors such as thermal migration, heat instability, light instability, non-biodegradability, toxicity, discoloration and the large amounts employed in order to be effective. Thus, there is always a demand for a material which will function as a flame retardant on poly(phenylene oxides) and concurrently will not, by incorporation therein, adversely aifect the chemical and/or physical and/or mechanical properties of the resultant poly(phenylene oxide) plastic composition.

The prior art problem of providing a flame retarded poly(phenylene oxide) composition having desired chemical, physical and mechanical properties has now been substantially solved by the present invention and the above described disadvantages substantially overcome.

Accordingly, one of the main objects of the present invention is to provide poly(phenylene oxide) plastic compositions which are flame retarded.

Another object of the present invention is to provide a material for poly(phenylene oxide) plastic compositions which will not substantially adversely affect the chemical and/ or physical and/ or mechanical properties of lsaid compositions.

A further object of the present invention is to provide a flame retardant which is economic and easy to incorporate into poly(phenylene oxide) plastics without being degraded or decomposed as a result of blending or processing operations.

It has been found that the foregoing objects can be obtained by the incorporation of a new class of halogenated aryl compounds in PPO to subsequently provide flame retarded compositions which exhibit outstanding chemical, physical and mechanical properties.

The halogenated aryl compounds used in the present invention compositions have the formula:

In Formula I above, Z is bromine or chlorine, m and m are integers each independently having a value of 1-5; 1 and i are integers each independently having a value of 0-2; M and M are each independent and are from the group oxygen, -NH and sulfur with the proviso that M and M cannot concurrently be oxygen in both cases; A is from the group chlorine, cyano (-CN), nitro (-NO lower alkoxy (e.g. -OCH OCZH lower alkyl (e.g. CH C H C H C H fluorine, dialkylamino e.g. N(CH N(C H phenyl (-C H halo-phenyl, benzyl (-CH C H and halo-benzyl; and R is from the group where w =1-6 CHr-C (O)CH;

where X=H, Cl, Br

(s) out-on rue-@0132 where S=saturated ring 3 4 In Formula I, i-l-m or i'+m' is not greater than 5. present invention halogenated aryl compounds are shown It is to be understood that all of the compounds falling below: Within the above Formula I and as heretofore defined are (I) generically described herein as halogenated aryl com- A; A1 P 5 z Q -MRM' 6 Z The halogenated aryl compounds are found to be comm m patible with and effective additives for various polymeric TABLE IContinued Compound number Z m m A l 2 R M M 2 2 0 --NH NH- H2O S OH:

2 2 CN 1 O 2 2 -0 CH; 1 4 4 -CH 1 3 3 2 S 1 1 C4Ho 1 O In general, the halogenated aryl compounds are prepared by reacting a halogenated phenol, thiophenol or aryl amine with a halogenated alkane at elevated temperatures in the presence of a basic material such as alkali metal hydroxides, carbonates, bicarbonates, oxides and hydrides. The preferred alkali metals are potassium and sodium. Where one desires to increase, for example, ease of handling the reaction mass, solvents such as ketones (e.g. acetone, methyl ethyl ketone, and methyl iso-butyl ketone), alcohols (e.g. methanol, ethanol, iso-propyl alcohol, butyl alcohols and glycols), aqueous solvents (e.g. water, a mixture of water and alcohol and a mixture of water and ketone), and polar aprotic solvents such as dimethylformarnide (DMF), dimethyl sulfoxide (DMSO) and ethers such as tetrahydrofuran (THF), can be employed. The desired end product i.e. the halogenated aryl compound, can be recovered from the reaction mass via various methods such as distillation or crystallization. Where the end product requires recovery via crystallization, various aromatic solvents such as benzene, toluene, xylene, dichlorobenzene and the like can be used.

Specifically, the symmetrical halogenated aryl compounds are prepared, for example, according to the following reactions:

(III) :t t ene ecw In the above reaction, X is halogen, preferably chlorine and R is the same as defined herein. Where m and m and i and i are different integers, then equivalent molar portions of the particular halogenated phenol, thiophenol or aryl amine are used with equivalent portions of dissimilar halogenated phenol, thiophenol or aryl amine.

The unsymmetrical halogenated aryl compounds are prepared, for example, according to the following reactions:

In the above reaction, X and R are the same as mentioned above.

The above reactions are conducted at temperatures ranging from the freezing point of the initial reaction mass to the boiling point thereof. Preferably the temperatures are from about 40 C. to about 200 C. and more preferably from about 50 C. to about C. It is to be understood that the reaction can be conducted under sub-atmospheric (e.g. 1/ 10-8/ 10 atmospheres), atmospheric or super-atmospheric (e.g. 1.5-10 atmospheres) pressure. Preferably, the reaction is carried out at atmospheric pressure.

The above-described processes can be carried out with conventional, readily available chemical processing equipment. For example, a conventional glass-lined vessel provided with heat transfer means, a reflux condenser and a mechanical stirrer can be advantageously utilized in practicing any of the preferred embodiments of the invention described in the examples set forth herein. The compounds described hereinabove are more fully described and illustrated in copending US. patent application Ser. No. 330,838, filed on Feb. 8, 1973, and incorporated.

The amount of halogenated aryl compound employed in the present invention compositions is any quantity which will effectively render the poly(phenylene oxide) containing composition flame retardant. In general, the amount used is from about 1% to 25% by weight, based on the total weight of the composition. Preferably, the

amount employed is from about to about by weight. It is to be understood that any amount can be used as long as it does not substantially adversely aifect the chemical and/ or physical and/ or mechanical properties of the end polymer composition. The amount utilized, however, is such amount which achieves the objectives described herein.

It is to be understood that the term poly(phenylene oxide) as used herein means products of the oxidative polymerization of phenols to poly (oxyphenylenes) which are also known as poly(phenylene oxides) or poly(phenylene ethers). This term also includes blends with other thermoplastics and/or plasticizers, however, the poly- (phenylene oxide) comprises in all cases at least 50% by weight of the blend.

Thus the poly(phenylene oxide) used in the present invention compositions is any poly(phenylene oxide) herein defined and which one so desires to flame retard. It is to be understood that the poly(phenylene oxide) used can be a virgin material, i.e. substantially free of additives such as stabilizers, plasticizers, dyes, pigments, fillers, and the like, or the poly(phenylene oxide) can have additives (such as those mentioned and described herein) already contained therein or added concurrently with or after the addition of the halogenated aryl compounds.

Another facet of the present invention relates to the use of certain metal compounds with the halogenated aryl compounds to promote a cooperative effect therebetween and thus enhance the flame retardancy of the resultant plastic composition as compared to the flame retardancy of either one component used separately. These enhancing agents are from the group antimony, arsenic, bismuth, tin and zinc-containing compounds. Without limitation, examples of said enhancing agents include Sb O SbCl SbBr SbI SbOCl, As O As O ZnBO BaB O -H O, 2-ZnO-3B O -H O and stannous oxide hydrate. The preferred enhancing agent is antimony trioxide.

The amount of enhancing agent employed in the present invention compositions is any amount which when used with said halogenated aryl compounds will promote a cooperative eflect therebetween. In general, the amount employed is from about 1% to about 15%, preferably from about 2% to about 10%, by weight, based on the total weight of plastic composition. Higher amounts can be used as long as the desired end result is achieved.

It is also within the scope of the present invention to employ other materials in the present invention compositions where one so desires to achieve a particular end result. Such materials include, without limitation, adhesion promoters; antioxidants; antistatic agents; antlmicrobials; colorants; flame retardants such as those listed on pages 456-458, Modern Plastics Encyclopedia, ibid. (in addition to the new class of flame retardants de scribed herein); heat stabilizers; light stabilizersz pigments; plasticizers; preservatives; ultraviolet stabilizers and fillers.

In this latter category, i.e. fillers, there can be mentioned without limitation, materials such as glass; carbon; cellulosic fillers (wood flour, cork and shell flour); calcium carbonate (chalk, limestone, and precipitated calcium carbonate); metal flakes; metallic oxides (aluminum, beryllium oxide and magnesia); metallic powders (aluminum, bronze, lead, stainless steel and zinc); polymers (comminuted polymers and elastomer-plastic blends); silica products (diatomaceous earth, noyaculite, quartz, sand, tripoli, fumed colloidal silica, sillca aerogel, wet process silica); silicates (asbestos, kaohnrte, mica, nephepiline syenite, talc, wollastonite, aluminum silicate and calcium silicate); and inorganic compounds such as barium ferrite, barium sulfate, molybdenum disulfide and silicon carbide.

The above mentioned materials, including fillers, are more fully described in Modern Plastics Encyclopedia,

i0 ibid., and which publication is incorporated therein (in toto) by reference.

The amount of the above described materials employed in the present invention compositions can be any quantity which will not substantially adversely affect the desired results derived from the present invention compositions. Thus, the amount used can be zero (0) percent, based on the total weight of the composition, up to that percent at which the composition can still be classified as a plastic. In general, such amount will be from about 0% to about 75% and specifically from about 1% to about The halogenated aryl compounds can be incorporated in to the poly(phenylene oxide) at any processing stage in order to prepare the present invention compositions. In general, this is undertaken prior to fabrication either by physical blending or during the process of forming poly(phenylene oxide) per se. Where one so desired, the halogenated aryl compounds may be micronized into finely divided particles prior to incorporation into the poly(phenylene oxide).

Example I A poly(phenylene oxide) (PPO) plastic material (GE 534-801, a product of General Electric Company and containing substantially no fillers) is utilized as the base resin in order to prepare 26 formulations (plastic compositions). With the exception of formulation No. 1, the particular halogenated aryl compound (and the antimony trioxide enhancing agent where indicated) is incorporated into the plastic by adding both to a Brabender mixer (Plastic-Corder, Torque Rheometer, Model PLV-150, C. W. Brabender Instruments Inc., South Hackensack, N.J.). The mixer is equipped with a pair of roller type blades positioned within a head provided with heat transfer means.

The resultant mixture is heated to about 320 C.; at this temperature, it is in a molten state. The percentages by weight of each component utilized in the respective formulations are listed in Table II. Each formulation is discharged from the mixer and upon cooling solidifies and is ground into chips. The chips are subjected to compression molding in a Wabash press by placing said chips between two platens, the bottom of which contains four equal size depressions three inches by five inches by inch deep. The top platen is then placed over the bottom platen and heat transfer means supplied thereto in order to melt said chips and thus provide solid samples (after cooling) for testing.

Portions of the samples of each respective formulation (Nos. 1-26) prepared according to the above de' scribed procedure are then subjected to two different standard flammability tests, i.e. UL 94 and ASTM D- 286370. The UL 94 is, in general, the application of a burner to a test specimen (strip) for a certain period of time and observation of combustion, burning, and extinguishment. This procedure is fully set forth in Underwriters Laboratories bulletin entitled UL 94, Standard for Safety, First Edition, September 1972 and which is incorporated herein by reference. ASTM No. D-2863- is a flammability test which correlates the flammability of a plastic specimen to the available oxygen in its immediate environment; this correlation is stated as an Oxygen Index, O.I., level predicated upon the percent oxygen in the gaseous medium which is required to just provide a steady state of continuous burning of the plastic specimen. This ASTM method is fully described in 1971 Annual Book of ASTM Standards-Part 27, published by the American Society For Testing and Materials, 1916 Race Street, Philadelphia, Pa.; this publication is to be considered as incorporated (in toto) herein by reference.

II The results of these flammability tests are shown in Table II.

TABLE II [Flammability data. for PP plastic compositions containing halogenated aryl compounds] Halogenated Enhancar yl compound ing agent Oxygen Formulation SbzOa, index, number Number Percent percent percent UL 9 1 O 0 25. SB 20 O 26. 5 SIS-2 20 I0 30. 5 SIB-0 20 0 28. 0 SE-l 20 38. 0 SE-O 20 0 28. 5 813-1 20 10 43. 5 SE0 2O 0 28. 5 SE-l 20 10 42. 5 SE() 20 0 29. 5 513-0 20 10 44. 5 SE-O 20 0 28. 0 S E-l 20 10 34. 5 8131-0 20 0 28. 5 812-1 20 10 33. 0 815-0 20 O 28.0 SE-1 20 10 34. 5 SE4) 20 0 28. 5 SE-l 20 10 33. 0 SE-O 20 0 29. 0 SE-O 20 10 44. 0 SE-O 20 0 28.0 813-1 20 10 34. 5 SE-O 20 O 28. 0 SE-l 20 10 33. O SE-O 20 10 41. 0 SE-O Referring to Table II, the halogenated aryl compound number relates to the structural formulae heretofore set forth in Table I; a difference of 2% in the Oxygen Index values is considered significant; and the UI. 94 values are on a graduated scale wherein the highest degree to lowest degree of flame retardancy is respectively SE-O, SE-l, SE-2, SB and Burns.

The results shown in Table II demonstrate the unique effectiveness of these halogenated aryl compounds as flame retardants for poly(phenylene oxide). Specifically, formulation No. l (the control) had an 0.1. of 25.5 and UL 94 value of SB. In the even numbered formulations, the use of the particular halogenated aryl compound results in a significant increase in fire retardancy as measured by 0.1. Formulation No. 1 had 21 SB rating, UL 94; however, the individual UL rating of SE-O for most of these formulations is, in this case, more indicative of increased flame retardancy.

The use of an enhancing agent such as Sb O to promote a cooperative effect between such agent and the halogenated aryl compound is fully demonstrated via the results obtained from testing the odd numbered formulations. The highest UL 94 ratings and significantly higher 01. values are obtained by the use of an enhancing agent.

Example II Example I is repeated twice; once using a 10% halogenated aryl compound level and 3% Sb O level and secondly, and 5% levels respectively. At both levels, the 0.1. values and UL 94 ratings are slightly lower than the %/10% levels of Example I.

Example III Portions of the solid samples of Formulation Nos. 1-26 prepared according to the above described procedure of Example I are subjected to the following ASTM tests in order to ascertain other properties of the resultant plastic composition:

(1) Tensile Strength (at break): ASTM Test No. D63 8- (2) Flexural Strength: ASTM Test No. D790-63;

(3) Flexural Modulus: ASTM Test No. D79063;

(4) Notched Izod Impact: ASTM Test No. D256-56;

and

(5) Heat Distortion Temperature (HDT): ASTM Test Each of the aforementioned ASTM Tests are standard tests in the art and are utilized collectively in order to ascertain the efficacy of a polymeric system as an overall flame retarded composition for commercial application. All of these ASTM tests are to be considered as incorporated herein by reference.

The results of these ASTM tests show that the physical properties of the present invention compositions are basically the same (except 0.1. and UL 94 values) as the plastic material without the flame retardant (i.e. formula tion No. 1). Thus, there is no substantial adverse effect on the physical properties of the plastic material when the novel compounds are incorporated therein.

Example IV The procedure of Examples I, II and III are repeated except that the enhancing agent used is zinc borate instead of Sb O Substantially the same results are obtained using zinc borate as those obtained using Sb O The other metal containing compounds are found to be equally eifective.

Example V Samples of each of Formulation Nos. 1 through 26 Table II, are subjected to temperature (thermal) stability tests via the use of thermal gravimetric analysis (TGA). This test employed the use of a Thermal Balance, model TGS-l, Perkin-Elmer Corporation, Norwalk, Connecticut and an electrical balance, Cahn 2580 model, Cahn Instrument Company, Paramount, Calif. The results of these tests show that the halogenated aryl compound containing Formulations had more than adequate stability for melt processing and subsequent heat aging (i.e. high temperature applications) and thus demonstrating that the particular halogenated aryl compounds are quite compatible with the plastic material. The halogenated aryl compound stability thus aids in providing sufiicient flame retardancy at the plastic decomposition temperature. This test also demonstrates that these comcompounds do not exhibit migration.

In view of the foregoing Examples and remarks, it is seen that the plastic compositions, which incorporate these compounds, possess characteristics which have been unobtainable in the prior art. Thus, the use of these compounds in the above described plastic material as flame retardants therefor is quite unique since it is not possible to predict the effectiveness and functionality of any particular material in any polymer system until it has actively undergone incorporation therein and the resultant plastic composition tested according to various ASTM Standards. Furthermore, it is necessary, in order to have commercial utility, that the resultant flame retarded plastic composition possess characteristics such as being nontoxic. Use of these compounds in the plastic material has accomplished all of these objectives.

The above examples have been described in the foregoing specification for the purpose of illustration and not limitation. Many other modifications and ramifications will naturally suggest themselves to those skilled in the art based on this disclosure. These are intended to be comprehended as within the scope of this invention.

What is claimed is:

I. A plastic composition containing poly(phenylene oxide) having incorporated therein a flame retardant which is a halogenated aryl compound having the forwherein Z is selected from the group consisting of bromine or chlorine; m and m are integers having a value of 1-5; 1 and i are integers having a 'value of 0-2; M and M are each independent and are selected from the group consisting of oxygen, -NH or sulfur with the proviso that M and M cannot concurrently be oxygen in both cases; A is selected from the group consisting of chlorine, cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl, or halo-benzyl; and R is selected from the group consisting of (a) alkylene group having from one to six carbon atoms where w 1-6 where X=H, Cl, Br

( om-o 0 011, CHzjil Hie- A0112 where S=saturated ring 2. The composition as set forth in claim 1 wherein i and i are both 0.

3. The composition as set forth in claim 1 wherein i and i' are both 1.

4. The composition as set forth in claim 1 wherein i and i are both 2.

5. A plastic composition containing poly(phenylene oxide) having incorporated therein a flame retardant which is a halogenated aryl compound having the formula:

Ai Ai' zmg naasgpi mzw wherein Z is selected from the group consisting of bromine or chlorine; m and m are integers having a value of 1-5; i and i are integers having a value of (l-2; A is selected from the group consisting of chlorine, cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl, or halo-benzyl; and R is selected from the group consisting of (a) alkylene group having from one to six carbon atoms where w=16 CHz-C (O)CH;

CHz-CH where S= saturated ring 6. The composition as set forth in claim wherein i and i are both 1.

7. The composition as set forth in claim 5 wherein i and z" are both 1.

8. The composition as set forth in claim 5 wherein i and i are both 2.

9. The composition as set forth in claim 6 wherein R is an alkylene group having from 1 to 6 carbon atoms.

10. A plastic composition containing poly(phenylene oxide) having incorporated therein a flame retardant which is a halogenated aryl compound having the formula:

whe

Where S=saturated ring 11. The composition as set forth in claim 10 wherein i and i' are both 0.

12. The composition as set forth in claim 10 wherein i and i are both 1.

13. The composition as set forth in claim 10 wherein i and z" are both 2.

14. The composition as set forth in claim 11 wherein R is an alkylene group having from 1 to 6 carbon atoms.

15. A plastic composition containing po1y(pheny1ene oxide) having incorporated therein a flame retardant which is a halogenated aryl compound having the forwherein Z is bromine or chlorine, in and m' are integers having a value of 1-5, i and i are integers having a value of 0-2; A is chlorine, cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl, or halo-benzyl; and R is selected from the group consisting of (a) alkylene group having from one to six carbon atoms where w=16 magi LH.

where X=H, Cl, Br

( CHz-C H where S=saturated ring 16. The composition as set forth in claim wherein i and i are both 0.

17. The composition as set forth in claim 15 wherein i and i are both 1.

18. The composition as set forth in claim 15 wherein i and i are both 2.

19. The composition as set forth in claim 16 wherein R is an alkylene group having from 1 to 6 carbon atoms.

20. A plastic composition containing poly(phenylene oxide) having incorporated therein a flame retardant which is a halogenated aryl compound having the formula:

wherein Z is bromine or chlorine, m and m are integers having a value of 1-5; i and i are integers having a value of 0-2; A is chlorine, cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl, or halo-benzyl; and R is selected from the group consisting of (a) alkylene group having from one to six carbon atoms (CHE)W""O (CHZ)W Where w =1-6 mgsm.

where X=H, Cl, Br

where S=saturated ring wherein Z is bromine or chlorine, in and m are integers having a value of 1-5; i and i are integers having a value of 0-2; A is chlorine, cyano, nitro, lower alkoxy, lower alkyl, fluorine; dialkylamino, phenyl, halo-phenyl, benzyl, or halo-benzyl; and R is selected from the group consisting of (a) alkylene group having from one to six carbon atoms Whore X=H, Cl, Br

( CHz-CH where S=saturated ring 26. The composition as set forth in claim 25 wherein i and i are both 0.

27. The composition as set forth in claim 25 wherein i and i are both 1.

28. The composition as set forth in claim 25 wherein i and i are both 2.

29. The composition as set forth in claim 26 wherein R is an alkylene group having from 1 to 6 carbon atoms.

References Cited UNITED STATES PATENTS 4/1972 Yonagi et al. ..l. 161403 2/ 1973 Kutner et al. 2 60'-45.95 G

M. J. WELSH, Primary Examiner US. Cl. X.R.

260-37 R, 37 M, 45.75 R, 45.95 G 

1. A PLASTIC COMPOSITION CONTAINING POLY(PHENYLENE OXIDE) HAVING INCORPORATED THEREIN A FLAME RETARDANT WHICH IS A HALOGENATED ARYL COMPOUND HAVING THE FORMULA: 